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CLAUS PROCESS
Manufacture of elemental Sulfur from Hydrogen Sulfide

Introduction: -

Claus process is the most common process used in the manufacturing of elemental Sulfur. The
process is very useful to recover Sulfur in elemental in the petroleum refineries. The Claus
process is the most significant gas desulfurizing process, recovering elemental sulfur from
gaseous hydrogen sulfide. Hydrogen sulfide occurs in many gas wells. It is produced in bulk
quantities in the desulfurization process of petroleum products where in the organic sulfur is
trapped as hydrogen sulfide. It is sent to a Claus plant where the sulfur is recovered and a low
grade steam is obtained. Hydrogen sulfide has been considered a liability which only
occasionally turned out to be an asset depending on the international sulfur price. Now the claus
process to obtain elemental sulfur has resulted in increase in the importance of hydrogen sulfide
making it an asset1.

The multi-step Claus process recovers sulfur from the gaseous hydrogen sulfide are also obtained
from by-product gases containing hydrogen sulfide derived from refining crude oil and other
industrial processes. The by-product gases mainly originate from physical and chemical gas
treatment units (Selexol, Rectisol, Purisol and amine scrubbers) in refineries, natural gas
processing plants and gasification or synthesis gas plants. These by-product gases may also
contain hydrogen cyanide, hydrocarbons, sulfur dioxide or ammonia. The most direct process of
obtaining hydrogen and sulfur from hydrogen sulfide is thermal decomposition, catalytically or
non catalytically. However, the reaction is highly endothermic and the equilibrium conversion
even at high temperatures is low (10%, 20% and 30% at 1143, 1283 and 1403K, respectively)1.

In this process H2S is selectively oxidized to sulphur over TiO2/SiO2 catalysts2. Claus process
consist of two reactions; thermal oxidation and catalytic reaction that are discussed further. In
order to provide a high selectivity to sulfur, reactions leading to SO need to be suppressed3.
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Reactions: -
• Main Reaction:-

• Combustion reaction:-

• Side Reactions:-

Assumptions: -
1. All the reactions are considered as conversion reactions.
2. In RC-1501 B the reactions from (iv) to (viii) are considered as series reactions as there is
no provision of Parallel reactions in DWSIM and conversion PFR are taken instead of a
furnace because there is no provision of furnace in DWSIM.
3. Two different S8 compounds were added into DWSIM database to match the stoichiometry.
(Compound creator wizard was used to add two S8 & S2 compounds in DWSIM data base).
Thermodynamic information of the created sulfur compounds were taken from literature.
4. Reaction (viii) is actually an equilibrium reaction and occurs after cooling in E 1504 but
as there is no provision of such condition in DWSIM, it is assumed that this reaction
occurs in RC-1501 B.
5. To maximize the Sulfur yield in downstream process (reactors) it is desired that only one
third of the H2S contained in the gases is oxidized to form a 2/1 ratio of H2S to SO2 in
reaction (ii).
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Brief Description: -
Raw material:

Air (Oxygen), SWS off gas (H2S, NH3, CO2), AGR unit gas (H2S, CO2, N2).

Product:

Sulfur in S8 form and in liquid state.

All the streams Oxygen (1), SWS off gas (2), AGR unit off gas (3), are first heated in a shell and
tube heat exchanger with process stream as high-pressure steam. These heated streams are then
blended together and sent to the reactor RC-1501 A and followed by reactor RC-1501 B. In real
process instead of using RC-1501 A and RC-1501 B rectors a single H-1501 reaction furnace is
used but as there is no provision of furnace in DWSIM conversion reactors RC-1501 A and RC-
1501 B are used4. In RC-1501A combustion reactions (ii) & (iii) occurs while reactions (iv) to
(viii) occurs in RC-1501 B.

The outlet streams of the reactor RC-1501 B ( RC_1501B outlet) is then sent to coolers E-1504
and E-1505 to drop the stream temperature to 195°C from 345°C.The stream E-1505 out (5) is
then sent to V-1501 to separate liquid Sulfur from the mixture of gaseous products and unreacted
reactants. The liquid stream obtained (viz V-1501 (liquid sulfur) (6)) is sent to storage. The
stream V-1501 (vapor) after getting heated in E-1506 is then sent to an alternate series of
reactors and R-1501 and R-1502 where reaction (i) takes place and separating vessel (v-1502 and
V-1503) where liquid S8 is separated from, reaction mixture. Then all the liquid sulfur streams
are then mixed in mixer (Liquid sulfur (S8) mixer) and sent to storage.
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Process Flow Diagram

Claus Process
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Flowsheet Description
The PFD of the Claus process is shown in Figure. In this report The Claus unit is designed such that
it can process acid and sour-water gases generated in the operation of an integrated gasification
combined cycle (IGCC) power plant5. It should be noted that elemental sulfur, in the operating
temperature range of the Claus unit, can exist as S2 and S8, among others. For the ease of simulation,
only these two sulfur species will be considered. Acid gas, Stream 2, from an acid-gas removal unit
and sour-water gas, Stream 3, from the sour-water stripper are preheated in E-1502 and E-1503,
respectively, with high-pressure steam and sent to the reaction furnace, H-1501, for combustion.
Preheated, enriched oxygen from an air separation unit (ASU) is used as the oxidizing agent in H-
1501. Incomplete combustion of hydrogen sulfide to sulfur dioxide is carried out in the furnace.
Since there is no provision of a furnace in DWSIM, we considered two conversion PFRs in series
suggested in the literature4. Additionally, partial combustion of ammonia can also take place. It is
desired that only one-third of the hydrogen sulfide contained in the gases be combusted to form a 2:1
ratio of hydrogen sulfide to sulfur dioxide. This 2:1 ratio of hydrogen sulfide to sulfur dioxide is
required to maximize sulfur yield in the downstream reactors. Primary combustion reactions within
H-1501 are given above. These highly exothermic reactions increase the temperature significantly (to
about 1450°C) in H-1501. Several side reactions take place as shown above.

The hot process gas is then cooled in E-1504 to generate high-pressure steam and to quench the
reactions taking place. At high operating temperatures, such as those in H-1501, sulfur exists
primarily as S2. Due to the equilibrium shift, the primary sulfur species present at the outlet of E-
1504 is S8. Further cooling is carried out in E-1505 by generating low-pressure steam. This
cooled process gas is then sent to V-1501 to separate the liquid sulfur. The process gas is then
sent to the first stage of a two-stage process. The process gas is heated in E-1506 with high-
pressure steam before being sent to the reactor R-1501, where hydrogen sulfide and sulfur
dioxide react in a 2/1 ratio to form elemental sulfur via Claus Reaction. The reactor effluent is
then cooled by generating low-pressure steam in E-1507. The liquid sulfur is then removed in V-
1502. The process gas is again preheated in E-1508 with high-pressure steam. The heated gas is
sent to the second-stage catalytic reactor R-1502. The reactor effluent is cooled in E-1509 using
cooling water to condense the formed sulfur. The process gas is then sent to a tail-gas treatment
unit (not modelled here)4.

Below is the table for output values which we get after simulating the above process in DWSIM
according to the above mentioned process flow diagram.
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Output Table

Stream Number 1 2 3 4 5 6 7 8
AGR unit off E-1504 E-1505 V-1501 (liquid
Name of the stream Oxygen SWS off gas E-1501 out R-1501 out
gas out out Sulfur)
Temperature(°C) 32 120 50 345 195 195 195 314
Pressure(bar) 10 2.4 2.1 1.7 1.3 16 16 1.3
Vapor Fraction 1 1 1 1 1 0 1 1
Mass Flow(tonne/h) 3.01 2.2 14.4 19.6 196 3.857 15.743 15.743
Mole Flow(kmol/h) 94.7 85.9 388.1 528.13 408.07 44.46 610.95 610.7

Component flow rates(kmol/h)

Hydrogen Sulfide 0 23.9 158.62842 0.78 0.609 0 0.6 0.012

Sulfur dioxide 0 0 0 30.5 23.53 0.000045 23.53 23.23
Water 0 0 5.3421645 528.13 408.07 31.42 376.64 377.29
Carbon dioxide 0 16.9 173.93573 117.68 90.93 0.00017 90.93 90.93
Carbon monoxide 0 2.1 0 75.42 58.27 0.00011 58.27 58.27
Oxygen 90 0 0 0 0 0 0 0
Hydrogen 0 10.2 0 0 0 0 0 0
Nitrogen 4.7 1.3 31.299978 37.3 28.82 0.0005 28.82 28.82
Ammonia 0 31.6 7.8521445 39.5 30.52 0.225 30.29 30.29

S2 0 0 0 0 0 0 0 0

S8 0 0 0 18.9 14.65 12.81 1.83 1.94

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Stream Number 9 10 11 12 13 14 15 16
E-1507 V-1502 V-1502 V-1502 V -1503 sulfur to
Name of stream E-1509 out To tail gas treatment unit
out liquid Vapor vapor out liquid storage
Temperature(°C) 175 108.25 175 234 160 160 160 170
Pressure(bar) 1.2 1.2 1.2 1 0.9 10 10 7.1
Vapor Fraction 1 0.33 0.99 0.99 0.99 0 0.99 0.017
Mass
15.743 0.00000012 15.743 15.743 15.743 1.29 14.45 5.149
Flow(tonne/h)
Mole
610.73 0.000000926 610.76 610.76 610.73 47.66 563.09 92.13
Flow(kmol/h)
Component flowrates(kmol/h)
Hydrogen Sulfide 0.012 2.23E-08 0.012 0.00024 0.00024 4.48E-10 0.0002 9.60E-10
Sulfur dioxide 23.2326 2.60E-08 23.23 23.22 23.22 4.27E-05 23.22 6.95E-08
Water 377.24 2.89E-07 377.24 377.25 377.25 4.55E+01 331.74 75.43
Carbon dioxide 90.93 2.72E-08 90.93 90.93 90.93 1.60E-04 90.92 2.70E-07
Carbon monoxide 58.27 2.65E-08 58.27 58.27 58.27 1.00E-04 58.27 1.73E-07
Oxygen 0 0 0 0 0 0 0 0
Hydrogen 0 0 0 0 0 0 0 0
Nitrogen 28.82 2.60E-08 28.82 28.82 28.82 5.29E-05 28.82 8.56E-08
Ammonia 30.29 8.02E-08 30.29 30.29 30.29 3.35E-01 29.96 0.45

S2 0 0 0 0 0 0 0 0

S8 1.94 4.31E-07 1.94 1.94 1.94 1.81E+00 0.12 14.63

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(A) References:-
1. Engineering, P. Production of hydrogen and sulfur from hydrogen sulfide. 41, 159–198
(1995).
2. Woo, S., Yeol, J. & Won, D. Selective oxidation of H 2 S to elemental sulfur. 16, 235–243
(1998).
3. Visser, L. M., Dillen, A. J. Van & Geus, J. W. SULFUR USING IRON OXIDE
CATALYSTS ON VARIOUS SUPPORTS. 17, 217–224 (1993).
4. Books, F. M. & Us, J. Ebooks Chemical Engineering.
5. Jones, D., Bhattacharyya, D., Turton, R. & Zitney, S. E. Rigorous Kinetic Modeling and
Optimization Study of a Modified Claus Unit for an Integrated Gasification Combined
Cycle ( IGCC ) Power Plant with CO 2 Capture. 2362–2375 (2012).

(B) References: -

1. Monnery, W. D., K. A. Hawboldt, A. Pollock, and W. Y. Svrcek, “New Experimental Data

and Kinetic Rate Expression for the Claus Reaction,” Chemical Engineering Science 55
(2000): 5141–5148.

2. Hawboldt, K. A., “Kinetic Modeling of Key Reactions in the Modified Claus Plant Front
End

3. Furnace,” Ph.D. thesis, Department of Chemical and Petroleum Engineering, University

of Calgary, Canada, 1998.

4. Monnery, W. D., K. A. Hawboldt, A. E. Pollock, and W. Y. Svrcek, “Ammonia Pyrolysis

and Oxidation in the Claus Furnace,” Ind. Eng. Chem. Res. 40 (2001): 144–151.

5. Perry, R. H., and D. W. Green, eds., Perry’s Chemical Engineers’ Handbook, 7th ed. (New
York: McGraw-Hill, 1997).